JPH11106448A - Liquid curable resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid storage-stable product which is good and has a low cured product having a low Young's modulus, but has excellent surface sticking properties, and is effective for coating requiring a low Young's modulus. To provide a liquid curable resin composition. SOLUTION: (1) (A) a polyol compound, (B)
30 to 80 parts by weight of a urethane (meth) acrylate obtained by reacting a polyisocyanate compound and (C) a hydroxyl group-containing (meth) acrylate compound, (2) a polymer containing a urethane bond and a (meth) acryloyl group in one molecule. Dimethylsiloxane compound 0.01 to 10
Parts by weight and 10 to 70 parts by weight of a polymerizable diluent containing a polymerizable monofunctional vinyl monomer copolymerizable with (3), components (1) and (2) [provided that component (1) and component (2)
And the total of component (3) is 100 parts by weight].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable liquid resin composition which provides a cured product having excellent liquid storage stability, low sticking property and low Young's modulus. More specifically, the present invention relates to a liquid curable resin composition suitable as a coating material for an optical fiber.

[0002]

2. Description of the Related Art In the production of an optical fiber, a resin coating is applied immediately after hot-melt spinning of a glass fiber for protection and reinforcement. As this resin coating, a two-layer coating structure is generally known in which a flexible primary coating layer is first provided on the surface of a glass fiber, and a secondary coating layer having higher rigidity is provided outside the primary coating layer. In order to put these resin-coated optical fibers into practical use, a so-called optical fiber tape in which several, for example, four or eight, are arranged on a plane and fixed with a binding material to form a rectangular tape-shaped structure. It is known to make core wires. And the resin composition for forming the primary coating layer is a soft material, the resin composition for forming the secondary coating layer is a hard material,
A binding material for bundling optical fiber wires to form a tape core wire is called a tape material. Further, a structure in which a tape core wire is further bound to form a multi-core tape is also known, and a binding material for this purpose is called a bundling material.

A curable resin used as a coating material for such an optical fiber must be liquid at room temperature and exhibit low viscosity with excellent coatability; the liquid material has good storage stability and composition distribution. Not hardening; fast curing and good productivity; sufficient strength and flexibility; little change in physical properties due to a wide range of temperature changes; heat resistance;
Excellent hydrolysis resistance; little change in physical properties over time; excellent long-term reliability; excellent resistance to chemicals such as acids and alkalis; low moisture absorption and water absorption; light resistance Characteristics such as excellent oil resistance; excellent generation of hydrogen gas that adversely affects the optical fiber; and the like.

[0004]

An optical fiber coated with a resin is wound and handled. At this time, it is necessary that the optical fiber can be smoothly wound or unwound without being stuck to a winding portion such as a pulley on a production line. The resin coating requires different physical properties depending on the portion of the resin coating, but an object of the present invention is to provide a liquid curable resin composition whose cured product has a low Young's modulus and a low sticking property. .

Another object of the present invention is to provide a cured product of the liquid curable resin composition of the present invention. Still other objects and advantages of the present invention will become apparent from the following description.

[0006]

According to the present invention, the above objects and advantages of the present invention are as follows: (1) (A) a polyol compound, (B) a polyisocyanate compound, and (C) a hydroxyl group-containing compound. Urethane (meth) acrylate obtained by reacting a (meth) acrylate compound 30 to 8
0 parts by weight, (2) 0.01 to 10 parts by weight of a polydimethylsiloxane compound containing a urethane bond and a (meth) acryloyl group in one molecule and copolymerizable with (3), components (1) and (2) 10 to 70 parts by weight of a polymerizable diluent containing a polymerizable monofunctional vinyl monomer [provided that the total of components (1), (2) and (3) is 100 parts by weight]. This is achieved by a liquid curable resin composition that is characterized.

The above composition is preferably characterized in that the cured product obtained by curing with radiation and / or heat has a Young's modulus at 23 ° C. of 10 kg / mm ² or less. T-peel strength of 50g / cm of two cured films bonded together
It can be characterized by: Secondly, the above objects and advantages of the present invention are achieved by a cured product obtained by curing the liquid curable resin composition of the present invention.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The urethane (meth) acrylate used as the component (1) of the present invention includes (A) a polyol compound,
It is produced by reacting (B) a polyisocyanate compound and (C) a hydroxyl group-containing (meth) acrylate compound. Examples of the reaction include a method in which a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate are charged at once and reacting them; a method in which a polyol and a polyisocyanate are reacted, and then a method in which the hydroxyl group-containing (meth) acrylate is reacted; Reacting the containing (meth) acrylate,
Then, a method of reacting a polyol, reacting a polyisocyanate and a hydroxyl group-containing (meth) acrylate,
Next, a method of reacting a polyol, and finally reacting a hydroxyl group-containing (meth) acrylate is used.

Here, the polyol of the component (A) includes
For example, polyether diol, polyester diol,
Polycarbonate diol, polycaprolactone diol and the like are used. These polyols can be used in combination of two or more kinds. The bonding mode of the structural units in these polyols is not particularly limited, and may be any of a random bond, a block bond, and a graft bond.

Examples of the polyether diol include, for example, ring-opening copolymerization of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol or two or more ion-polymerizable cyclic compounds. And polyether diols obtained by the reaction. Examples of the ionic polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran,
Methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide And cyclic ethers such as phenyl glycidyl ether, butyl glycidyl ether and glycidyl benzoate. Specific combinations of the two or more ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, and butene-1-oxide and ethylene oxide. A binary copolymer such as tetrahydrofuran, butene-1-oxide and ethylene oxide;
Ternary copolymers such as tetrahydrofuran, butene-1-oxide and ethylene oxide can be mentioned.
Further, a polyether diol obtained by ring-opening copolymerization of the ion-polymerizable cyclic compound and cyclic imines such as ethylene imine, β-propiolactone, cyclic lactones such as glycolic acid lactide, or dimethylcyclopolysiloxanes. Can also be used. The ring-opening copolymers of these ionic polymerizable cyclic compounds may be randomly bonded or may be in a block-like bond.

Among the above polyether diols, commercially available products include, for example, PTMG1000, PTMG2000
(Mitsubishi Chemical Corporation), PPG1000, EXC
ENOL 2020, 1020 (above, Asahi Ohlin Co., Ltd.)
PEG1000, Unisafe DC1100, DC
1800 (all manufactured by NOF Corporation), PTG100
0, PTG2000, PTG3000, PPTG200
0, PPTG1000, PTGL1000, PTGL2
000 (all made by Hodogaya Chemical Industry Co., Ltd.), Z-30
01-4, Z-3001-5, PBG2000A, PB
G2000B (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

Examples of the polyester diol include a polyester diol obtained by reacting a polyhydric alcohol with a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 3-methyl. -1,5-pentanediol, 1,9-nonanediol,
2-methyl-1,8-octanediol and the like. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like.

Commercially available polyester diols include, for example, Clapol P-2010 and P-101.
0, L-2010, L-1010, A-2010, A-
1010, F-2020, F-1010, PMIPA-
2000, PKA-A, PNOA-2010, PNOA
-1010 (all manufactured by Kuraray Co., Ltd.) and the like.

Examples of the polycarbonate diol include polycarbonate of polytetrahydrofuran, poly (hexanediol carbonate), poly (nonanediol carbonate), and poly (3-methyl-1,
5-pentamethylene carbonate) and the like.

Among the above polycarbonate diols, commercially available products include, for example, DN-980, DN-981, DN-9
-982, DN-983 (all made by Nippon Polyurethane Co., Ltd.), PMC-2000, PMC-1000, P
NOC-2000, PNOC-1000 (above, Inc.
Kuraray), Plaxel CD220, CD210, CD
220PL, CD210PL, CD220HL, CD2
10HL (all manufactured by Daicel Chemical Industries, Ltd.), PC-
8000 (US PPG), PC-THF-CD (B
ASF).

Examples of the polycaprolactone diol include, for example, polycaprolactone diol obtained by reacting ε-caprolactone with a diol. Examples of the diol include ethylene glycol, polyethylene glycol, propylene glycol,
Examples thereof include polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-butanediol.

Commercially available polycaprolactone diols include, for example, Placcel 240, 230, 23
0ST, 220, 220ST, 220NP1, 212,
210, 220N, 210N, L230AL, L220
AL, L220PL, L220PM, L212AL (all manufactured by Daicel Chemical Industries, Ltd.) and the like.
As the polyol other than the above as the component (A), for example, ethylene glycol, propylene glycol,
4-butanediol, 1,5-pentanediol, 1.6
-Hexanediol, neopentyl glycol, 1.4
-Cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, a dimethylol compound of dicyclopentadiene, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, β-methyl-δ
-Valerolactone ring-opening polymer, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified diol, polydimethylsiloxane-terminated diol compound, polydimethylsiloxane carbitol-modified diol, and the like.

It is also possible to use a diamine together with the above-mentioned polyol. Examples of such a diamine include diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4′-diaminodiphenylmethane, diamines containing a hetero atom, and polyether diamines.

The preferred molecular weight of the polyol is usually from 50 to 15,000, particularly preferably from 1,000 to 8,000, in terms of the number average molecular weight in terms of polystyrene. Further, as the polyisocyanate compound of the component (B),
For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-
Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3 '
-Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate,
3,3′-dimethylphenylene diisocyanate,
4′-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate,
Methylene bis (4-cyclohexyl isocyanate),
2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6
-Isopropyl-1,3-phenyl diisocyanate,
4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate,
Lysine isocyanate; These polyisocyanate compounds may be used alone or in combination of two or more.

Furthermore, the hydroxyl group-containing (meth) component (C)
As the acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4- Butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, tri Methylol propane di (meth) acrylate, trimethylol ethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, the following formula ( ) Or _{(2) H 2 C = C} (R 1) COOCH 2 CH 2 (OCOCH 2 CH 2 CH 2 CH 2 CH 2) n OH ··· (1) H 2 C = C (R 1) COOCH 2 CH (OH) CH ₂ OC ₆ H ₅ (2) (wherein, R ¹ represents a hydrogen atom or a methyl group, and n is 1
(Indicating the number of 1 to 15). Further, a compound obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid can be used in the same manner. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

In the production of the urethane (meth) acrylate (1), the proportion of each of the polyol (A), the polyisocyanate compound (B) and the hydroxyl group-containing (meth) acrylate (C) is determined based on the ratio of the hydroxyl group contained in the polyol. It is preferable that the isocyanate group contained in the polyisocyanate compound is 1.1 to 3 equivalents and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is 0.1 to 1.5 equivalents relative to the equivalent. In the reaction of the above three components, a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, and triethylenediamine-2-methyltriethyleneamine is usually used as a reaction reagent. Is used in an amount of 0.01 to 1% by weight based on the total amount of The reaction is usually carried out at a temperature of preferably from 10 to 90C, particularly preferably from 30 to 80C.

The preferred number average molecular weight of the urethane (meth) acrylate (1) used in the present invention is from 100 to 2
000, and particularly preferably 500 to 15,000. When the number average molecular weight of the urethane (meth) acrylate is less than 100, the Young's modulus of the obtained cured product tends to increase, and conversely, the number average molecular weight is 20,000.
If it exceeds 0, the viscosity of the composition becomes high and it becomes difficult to handle.

The urethane (meth) thus obtained
The compounding ratio of the acrylate in the composition of the present invention is 3 based on the total weight of the components (1), (2) and (3).
0 to 80% by weight. In order to maintain coatability when coating the optical fiber, flexibility of the coating material after curing, and long-term reliability at a higher level, the content is more preferably 40 to 70% by weight. If the proportion of the component (1) is less than 30% by weight, the toughness of the resulting composition will decrease, and if it exceeds 80% by weight, the viscosity of the composition will increase and the handleability will deteriorate.

The polydimethylsiloxane compound having a urethane bond and a (meth) acryloyl group in one molecule, which is used as the component (2) in the present invention, has a polyisocyanate compound and a hydroxyl group at at least one terminal, which will be described later. It is produced by reacting a reactive silicone compound with a hydroxyl group-containing (meth) acrylate.

As the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate used here, the compounds described above with respect to the component (1) can be used. The polydimethylsiloxane structure for forming the polydimethylsiloxane compound used in the present invention is introduced using a silicone compound having a hydroxyl group at at least one terminal and a non-reactive organic group at at least one terminal. Is done.

As such a silicone compound, for example, a 3- (2′-hydroxyethoxy) propyl group, a 3- (2 ′, 3′-hydroxypropyloxy) propyl group or a 3- (2′-ethyl) -2'-hydroxymethyl-3-hydroxy) propyl group and 3-
One end has a hydroxyl group, such as polydimethylsiloxane having an organic group such as (2'-hydroxy-3'-isopropylamino) propyl group and an unreactive organic group such as a trimethylsilyloxy group at the other end. Having a silicone compound. These may be used alone or in combination of two or more.

Commercially available silicone compounds having a hydroxyl group at one end as described above include, for example, Silaprene F
M-0411, FM-0421, FM-0425, FM
-D411, FM-D421, FM-D425 (above,
Chisso Corporation), TSL9105 (Toshiba Silicone Corporation), Shin-Etsu Silicone X-22-170A, X-
22-170B, X-22-170D, X-22-17
6B, X-22-176D, X-22-176DX, X
-22-178A and X-22-178B (all manufactured by Shin-Etsu Chemical Co., Ltd.).

The reaction for obtaining the above-mentioned polydimethylsiloxane compound includes, for example, a method in which a silicone compound having a hydroxyl group, a polyisocyanate compound and a (meth) acrylate containing a hydroxyl group are charged together and reacted; A method of reacting and then reacting a hydroxyl group-containing (meth) acrylate; a method of reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate, and then reacting the silicone compound.
It is preferable that the reaction is performed so that the total equivalent of the hydroxyl groups of the silicone compound having a hydroxyl group and the hydroxyl group-containing (meth) acrylate substantially matches the isocyanate equivalent of the polyisocyanate.

Further, by adding a polyol to the starting material of the above reaction, a structure such as a polyurethane polyol can be introduced between the polydimethylsiloxane structure and the (meth) acryloyl group. Examples of the polyol used here include the compounds described above for the component (1). Two or more of these polyols can be used in combination.

As a method for obtaining a polydimethylsiloxane compound having a polyol structure, for example, a method in which a silicone compound having a hydroxyl group, a polyol, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate are simultaneously reacted; a polyol and a polyisocyanate compound And then reacting the silicone compound and a hydroxyl group-containing (meth) acrylate; reacting the silicone compound, polyisocyanate compound and a hydroxyl group-containing (meth) acrylate, and then reacting a polyol; a polyisocyanate compound and the above A method in which a silicone compound is reacted, then a polyol is reacted, and finally, a hydroxyl group-containing (meth) acrylate is reacted; polyisocyanate and hydroxyl group-containing (meth) Reacting the acrylate, and then reacting the polyol, and finally a method of reacting the silicone compound, and the like.

As described above, the (meth) acryloyl group in the polydimethylsiloxane compound used in the present invention is introduced only at one terminal of the polydimethylsiloxane structure. When a (meth) acryloyl group is introduced into a plurality of terminals of the polydimethylsiloxane structure, a low sticking property cannot be obtained. The polydimethylsiloxane compound (2) used in the present invention has a polystyrene reduced number average molecular weight of 80.
It is preferably from 0 to 15,000, particularly 1,000.
A range of ~ 7,000 is preferred. Number average molecular weight is 800
If the number average molecular weight exceeds 15,000, the composition containing the liquid storage stability may be poor. May be inferior.

The polydimethylsiloxane compound used in the present invention is contained in the liquid curable resin composition in an amount of 0.01 to 10% by weight based on the total weight of the components (1), (2) and (3). Included in. Particularly, the range of 0.05 to 5% by weight is preferable. If the content of the polydimethylsiloxane compound is less than 0.01% by weight, the sticking property of the cured product may not be good, and if it exceeds 10% by weight, the liquid storage stability may be poor.

Component (3) of the present invention comprises component (1),
A polymerizable monofunctional vinyl monomer having one polymerizable vinyl group in the molecule or a polymer having a plurality of polymerizable vinyl groups in the molecule other than the components (1) and (2) copolymerizable with (2). It is a polymerizable diluent selected from a combination with a functional polyfunctional vinyl monomer.

Among the polymerizable diluents of the component (3) of the present invention, examples of the polymerizable monofunctional vinyl monomer include N-
Vinyl monomers such as vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole and vinylpyridine; isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate,
Acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl ( (Meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth)
Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate,
Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) Acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyp Propylene glycol (meth)
Acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth)
Acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N,
N-dimethylaminopropyl (meth) acrylamide,
Hydroxybutyl vir ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether and the following formulas (3) to (5) CH ₂ 2C (R ² ) -COO (R ³ O) _m -R ⁴ (3) (Wherein, R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 6, preferably 2 to 4 carbon atoms,
R ⁴ represents a hydrogen atom or an organic group having 1 to 12 carbon atoms or an aromatic ring, and m represents 0 to 12, preferably 1 to 8
Indicates the number of

[0035]

Embedded image (Wherein, R ² has the same meaning as described above, and R ⁵ has 2 to 2 carbon atoms.
8, preferably 2 to 5 alkylene groups, p is 1 to
8, preferably 1 to 4)

[0036]

Embedded image (Wherein R ² , R ⁵ and p have the same meaning as described above,
⁶ represents a hydrogen atom or a methyl group).

Commercially available polymerizable monofunctional vinyl monomers include, for example, Aronix M102, M110, M1
11, M113, M117 (Toa Gosei Co., Ltd.)
Manufactured), LA, IBXA, viscote # 190, # 19
2, # 2000 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Light acrylate EC-A, PO-A, NP-4E
A, NP-8EA, M-600A, HOA-MPL (all manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD TC11
OS, R629, R644 (all manufactured by Nippon Kayaku Co., Ltd.)
And the like.

Examples of polymerizable polyfunctional vinyl monomers include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) Acrylate, Tris (2
-Hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, bis (hydroxymethyl) tricyclodecanedi (meth) acrylate, addition of ethylene oxide or propylene oxide of bisphenol A Di (meth) acrylate of diol which is an isomer, di (meth) acrylate of diol which is an adduct of ethylene oxide or propylene oxide of hydrogenated bisphenol A, epoxy obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A Examples include (meth) acrylates, diacrylates of polyoxyalkylenated bisphenol A, and acrylate compounds such as triethylene glycol divinyl ether.

Commercially available polymerizable polyfunctional vinyl monomers include, for example, Iupimer UV SA1002, SA200
7 (manufactured by Mitsubishi Chemical Corporation), Viscort # 19
5, # 230, # 215, # 260, # 335HP, #
295, # 300, # 700 (Osaka Organic Chemical Industry Co., Ltd.)
Made), light acrylate 4EG-A, 9EG-A,
NP-A, DCP-A, BP-4EA, BP-4PA,
PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD R-604, DPC
A-20, -30, -60, -120, HX-620,
D-310, D-330 (all manufactured by Nippon Kayaku Co., Ltd.),
Aronix M-208, M-210, M-215,
M-220, M-240, M-305, M-309, M
-315 and M-325 (all manufactured by Toagosei Co., Ltd.).

These polymerizable diluents are preferably incorporated in the entire resin composition in an amount of 10 to 70% by weight, particularly 15 to 50% by weight. If it exceeds 70% by weight, sufficient toughness cannot be imparted to the cured product, which is not preferred. The polymerizable monofunctional vinyl monomer and the polymerizable polyfunctional vinyl monomer in the polymerizable diluent are 60-100 / 40-
0, preferably 65-100 / 35-0. If the proportion of the polymerizable monofunctional vinyl monomer is less than 60% by weight, the Young's modulus increases, and the properties required by the cured product of the present invention may not be obtained.

The liquid curable resin composition of the present invention is cured by heat and / or radiation. Here, radiation means infrared, visible light, ultraviolet, X-ray, electron beam, α-ray,
β rays, γ rays, etc. The liquid curable resin composition of the present invention can be used by adding a polymerization initiator. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used.

When the liquid curable resin composition of the present invention is thermally cured, a thermal polymerization initiator such as a peroxide or an azo compound is usually used. Specific examples include benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile, and the like.

When the liquid curable resin composition of the present invention is cured by radiation, a photopolymerization initiator is used, and if necessary, a photosensitizer is further added. Here, as the photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-
Phenylacetophenone, xanthone, fluorenone,
Benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, Benzyl dimethyl ketal,
1- (4-isopropylphenyl) -2-hydroxy-
2-methylpropan-1-one, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6
-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. Commercially available photopolymerization initiators include, for example, IRGACURE 184,
369, 651, 500, 907, CGI 1700, C
GI1750, CGI11850, CG24-61 (all manufactured by Ciba Geigy), Lucirin LR8728
(Manufactured by BASF), Darocur 116, 1173
(Manufactured by Merck), Ubecryl P36 (manufactured by UCB) and the like.

Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Isoamyl dimethylaminobenzoate and the like. Commercially available products include, for example, Ubecryl P102, 103, 104, 105 (above, UCB
Manufactured). When the liquid curable resin composition of the present invention is cured by using both heat and radiation, the thermal polymerization initiator and the photopolymerization initiator can be used in combination. The polymerization initiator is preferably incorporated in the entire composition in an amount of 0.1 to 10% by weight, particularly 0.5 to 7% by weight based on the total weight of the components (1), (2) and (3).

The liquid curable resin composition of the present invention may contain, if necessary, other curable oligomers or polymers in addition to the above components, as long as the properties of the liquid curable resin composition of the present invention are not impaired. Can be blended. Other curable oligomers or polymers described above include, for example, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, (meth) acrylate
Examples thereof include a siloxane polymer having an acryloyloxy group, and a reactive polymer obtained by reacting a copolymer of glycidyl methacrylate with another polymerizable monomer with (meth) acrylic acid.

Further, the liquid curable resin composition of the present invention may be used in combination with an amine in order to suppress the generation of hydrogen gas which causes transmission loss of an optical fiber.
Examples of such amines include diallylamine, diisopropylamine, diethylamine, diethylhexylamine and the like.

In addition to the above components, various additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, coating surface improvers, thermal polymerization inhibitors, leveling agents, surfactants, coloring agents , Storage stabilizers, plasticizers, lubricants, solvents,
Fillers, antioxidants, wetting improvers, and the like can be added as necessary. Here, as the antioxidant,
For example, Irganox 1010, 1035, 1076,
1222 (all made by Ciba-Geigy), Antigene
P, 3C, FR, GA-80 (Sumitomo Chemical Co., Ltd.)
UV absorbers include, for example, Ti
nuvin P, 234,320,326,327,3
28, 329, 213 (all made by Ciba Geigy), Se
esorb 102, 103, 110, 501, 202,
712 and 704 (all manufactured by Cipro Kasei Co., Ltd.); and as the light stabilizer, for example, Tinuvin 29
2, 144, 622LD (all manufactured by Ciba Geigy), Sanol LS770 (manufactured by Sankyo), Sumisorb
TM-061 (manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane. SH6062, 60 as commercial products
30 (manufactured by Dow Corning Silicone Toray Co., Ltd.), KBE903, 603, and 403 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the coating surface improver include dimethylsiloxane polyether and the like. And silicone additives such as DC-57 and D
C-190 (all made by Dow Corning), SH-28P
A, SH-29PA, SH-30PA, SH-190
(Toy Dow Corning Silicone Co., Ltd.
KF351, KF352, KF353, KF35
4 (all manufactured by Shin-Etsu Chemical Co., Ltd.), L-700, L-
7002, L-7500, FK-024-90 (or more,
Nippon Unicar Co., Ltd.).

The viscosity of the liquid curable resin composition of the present invention is
Usually 200 to 20,000 cp / 25 ° C, especially 2,000
~ 15,000 cp / 25 ° C is preferred. The cured product obtained by curing the liquid curable resin composition of the present invention with radiation or heat has a Young's modulus at 23 ° C. of 10 kg / mm.
^It is preferably ² or less. It is more preferably at most 5 kg / mm ^2, particularly preferably at most 3 kg / mm ² .

Further, the T-peel strength of a laminate of two cured cured films is preferably 50 g / cm. If the T-peel strength is higher than 50 g / cm, when the fibers are produced, the cured products adhere to each other or to the winding portion of the device, and the fibers cannot be produced smoothly. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the following, parts are indicated by weight%.
Means

Synthesis Example 1 of Component (1) Urethane (meth) acrylate Tolylene diisocyanate 1 was placed in a reaction vessel equipped with a stirrer.
3.5% by weight, 0.08% by weight of di-n-butyltin dilaurate, 0.02% of 2,6-di-t-butyl-p-cresol
% By weight and cooled to 5-10 ° C. While stirring, 9.0% by weight of 2-hydroxyethyl acrylate was added dropwise so that the temperature was maintained at 10 ° C or lower. After dropping,
The reaction was performed at 30 ° C. for 1 hour. Next, a number average molecular weight of 2.0
Then, the reaction was continued at 50-70 ° C. for 2 hours, and the reaction was terminated when the residual isocyanate became 0.1% by weight or less. The urethane acrylate obtained by this method is converted to U
A-1.

(1) Synthesis Example 2 of Urethane (meth) acrylate Component Tolylene diisocyanate 1 was placed in a reaction vessel equipped with a stirrer.
1.0% by weight, 0.08% by weight of di-n-butyltin dilaurate, 0.02% of 2,6-di-t-butyl-p-cresol
% By weight and cooled to 5-10 ° C. While stirring, 4.9% by weight of 2-hydroxyethyl acrylate was added dropwise so that the temperature was maintained at 10 ° C or lower. After dropping,
The reaction was performed at 30 ° C. for 1 hour. Next, a number average molecular weight of 2.0
Then, the reaction was continued at 50 to 70 ° C. for 2 hours, and the reaction was terminated when the residual isocyanate became 0.1% by weight or less. The urethane acrylate obtained by this method is converted to U
A-2.

Synthesis Example 1 of Component (2) Polydimethylsiloxane Compound A reaction vessel equipped with a stirrer was charged with 12.0% by weight of tolylene diisocyanate and 1,200 hydroxyl equivalents of α- [3-
(2′-hydroxyethoxy) propyl], 79.9% by weight of ω-trimethylsilyloxypolydimethylsiloxane, and 0.2% of 2,6-di-tert-butyl-p-cresol.
02 parts were charged and cooled to 5 to 10 ° C. When the temperature was lowered to 10 ° C or lower while stirring, 0.08 parts of di-n-butyltin dilaurate was added, and the mixture was stirred for 1 hour while controlling the liquid temperature at 20 to 30 ° C. Stirred for hours. Then, 2-hydroxyethyl acrylate 8.0
The reaction was continued at 50 to 70 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate became 0.1% by weight or less. The obtained polydimethylsiloxane compound had a number average molecular weight of 180 (the number average molecular weight in terms of polystyrene was measured by gel permission chromatography using HLS-8020 manufactured by Tosoh Corporation; the same applies hereinafter).
It was 0. The resin solution of the polydimethylsiloxane compound obtained by this method was designated as SA-1.

Synthesis Example 2 of Polydimethylsiloxane Compound as Component (2) In a reaction vessel equipped with a stirrer, 6.2% by weight of tolylene diisocyanate and 2,500 hydroxyl equivalents of α- [3- (2 ′
-Hydroxyethoxy) propyl], 89.6% by weight of ω-trimethylsilyloxypolydimethylsiloxane, and 0.02 part of 2,6-di-t-butyl-p-cresol were charged and cooled to 5 to 10 ° C. . When the temperature was lowered to 10 ° C or lower while stirring, 0.08 parts of di-n-butyltin dilaurate was added, and the mixture was stirred for 1 hour while controlling the liquid temperature at 20 to 30 ° C. Stirred for hours. Next, 4.2% by weight of 2-hydroxyethyl acrylate was added, and the reaction was continued at 50 to 70 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate became 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound was 5,200. The resin solution of the polydimethylsiloxane compound obtained by this method was designated as SA-2.

Examples 1 to 5 and Comparative Examples 1 to 4 Each component having the composition shown in Table 1 was charged into a reaction vessel equipped with a stirrer and stirred for 3 hours while controlling the temperature at 50 to 70 ° C.
A liquid curable resin composition was obtained.

Test Example The liquid curable resin composition shown in the above example was cured by the following method to prepare a test piece, which was evaluated as follows. The results are shown in Table 1.

1. Measurement of Young's Modulus A liquid curable resin composition was applied on a glass plate using an applicator bar having a thickness of 250 μm. This was irradiated with ultraviolet rays having an energy of 1 J / cm ² in air. This cured product was heated at room temperature 23 ° C. and 50% relative humidity in an atmosphere of 12%.
After conditioning for more than an hour, test specimens were prepared. JIS
According to K7113, the Young's modulus at 23 ° C. was measured. However, the pulling speed was 1 mm / min, and 2.
The Young's modulus was calculated from the tensile stress at 5% strain.

2. Measurement of Surface Sticking Property (T-Peel Strength) The liquid curable resin composition was applied on a glass plate using an applicator bar having a thickness of 150 μm. This was irradiated with ultraviolet rays having an energy of 0.5 J / cm ² in air.
Immediately after the irradiation, the surfaces of the cured products were adhered to each other, and the cured product was loaded with a load of 1 kg for 5 minutes, and then conditioned at room temperature of 23 ° C. and 50% relative humidity for 6 hours or more. After the condition adjustment, the bonded cured product was cut at a width of 2 cm to obtain a test piece. As the surface sticking property, T peel strength at 23 ° C. was measured. The pulling speed is 500mm /
min, and the strength (g / cm) per 1 cm width was calculated.

3. Measurement of Liquid Storage Stability The liquid storage stability of the liquid curable resin composition was determined by leaving the resin at 60 ° C. for 30 days, then dropping the resin liquid on a glass plate, and separating the liquid surface. Observed visually. Table 1 shows the evaluation results.

[0059]

[Table 1]

[0060]

Industrial Applicability The liquid curable resin composition of the present invention is excellent in liquid storage stability, has excellent surface sticking properties, and has a low Young's modulus, although the cured product has a low Young's modulus. It is effective for surface materials that require Preferred embodiments of the present invention will be listed below. 1) The component (3) comprises a polymerizable monofunctional vinyl monomer having one polymerizable vinyl group in the molecule and a polymerizable polyfunctional vinyl monomer having a plurality of polymerizable vinyl groups in the molecule. A liquid curable resin composition having a functional vinyl monomer / polymerizable polyfunctional vinyl monomer weight ratio of 65 to 100/35 to 0. 2) an organic group containing at least two urethane bonds and at least one (meth) acryloyl group at one end, and the other end blocked with a non-reactive organic group has a number average molecular weight of 800 to 15, A liquid curable resin composition containing 000 polydimethylsiloxane compounds. 3) A liquid curable resin composition wherein the polydimethylsiloxane compound is formed by the reaction of a silicone compound having a hydroxyl group at one end, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate. 4) An optical fiber coating obtained by curing the liquid curable resin composition of the present invention.

Continuing from the front page (72) Inventor Komiya All 11-11-24 Tsukiji, Chuo-ku, Tokyo Japan Gosei Rubber Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Seiko Rubber Co., Ltd.

Claims (5)

[Claims] (1) 30 to 80 parts by weight of a urethane (meth) acrylate obtained by reacting (1) (A) a polyol compound, (B) a polyisocyanate compound, and (C) a hydroxyl group-containing (meth) acrylate compound; A) a polydimethylsiloxane compound containing a urethane bond and a (meth) acryloyl group in one molecule;
Parts by weight, and 10 to 70 parts by weight of a polymerizable diluent containing a polymerizable monofunctional vinyl monomer copolymerizable with (3) component (1) and component (2) [provided that component (1) and component (2) And the total of component (3) is 100 parts by weight]. 2. A polymerizable difunctional diluent (3) is used together with the polymerizable monofunctional vinyl monomer to form a polymerizable polyfunctional vinyl monomer copolymerizable with the components (1) and (2). 2. The liquid curable resin composition according to claim 1, wherein the composition contains 40% by weight or less based on the total weight of the vinyl monomer and the polymerizable polyfunctional vinyl monomer. 3. The cured product obtained by curing with radiation and / or heat has a Young's modulus at 23 ° C. of 10 kg / mm.
The liquid curable resin composition according to claim 1, which is ² or less. 4. When two cured films obtained by curing with radiation and / or heat are superposed on each other on a cured surface, the T-peel strength of the mating surface is 50 g / cm or less. The liquid curable resin composition according to the above. 5. A cured product obtained by curing the liquid curable resin composition according to claim 1, 2, 3, or 4.